Resin composition, cured film, laminated film, and method for manufacturing semiconductor device

Abstract

[Problem] To provide a highly heat resistant resin composition which exhibits good tackiness at low temperatures less than or equal to 180 C., and whose production of a volatile portion due to decomposition or the like is small even at high temperatures greater than or equal to 250 C., and whose increase in adhesive force is small even after passage through a heat treatment step, and therefore which allows a base material to be easily peeled off at room temperature when the base material is to be peeled off, and a cured membrane and a laminate film that employ this resin composition. [Solution Means] A resin composition containing a polyimide-based resin and a methylol-based compound, the resin composition being characterized in that the polyimide-based resin has an acid dianhydride residue and a diamine residue, and has as the diamine residue at least a residue of a polysiloxane-based diamine represented by General formula (1) and a residue of an aromatic diamine having a hydroxyl group, and a cured product and a laminate film that employ this resin composition. ##STR00001##
(n is a natural number, and an average value thereof calculated from an average molecular weight of the polysiloxane-based diamine is in a range of 5 to 30. R.sup.1 and R.sup.2 may be individually the same or different, indicating an alkylene group or a phenylene group whose carbon number is 1 to 30. R.sup.3 to R.sup.6 may be individually the same or different, indicating an alkyl group, a phenyl group or a phenoxy group whose carbon number is 1 to 30.)

Claims

1. A resin composition containing a polyimide-based resin and a methylol-based compound, wherein the polyimide-based resin has an acid dianhydride residue and a diamine residue; the diamine residue is at least a residue of a polysiloxane-based diamine represented by general formula (1) and a residue of an aromatic diamine having an hydroxyl group, ##STR00009## wherein n is a natural number, and an average value thereof calculated from an average molecular weight of the polysiloxane-based diamine is in a range of 5 to 30, R.sup.1 and R.sup.2 may be individually the same or different and indicate an alkylene group or a phenylene group having a carbon number that is 1 to 30, R.sup.3 to R.sup.6 may be individually the same or different and indicate an alkyl group, a phenyl group or a phenoxy group having a carbon number that is 1 to 30; and the resin composition has a glass transition temperature after curing that is less than or equal to 40 C.

2. The resin composition according to claim 1, containing as the diamine residue the residue of the polysiloxane-based diamine represented by general formula (1) at greater than or equal to 40 mol % in a total amount of the diamine residue.

3. The resin composition according to claim 1, containing as the diamine residue the residue of the aromatic diamine having a hydroxyl group at 1 to 40 mol % in a total amount of the diamine residue.

4. The resin composition according to claim 3, wherein the aromatic diamine having an hydroxyl group is an aromatic diamine represented by any one of General formulas (2) to (5) below: ##STR00010## wherein at least one of R.sup.7 to R.sup.10 is a hydroxyl group, and the others may be the same or different, indicating a group selected from a hydrogen atom, an alkyl group having a carbon number that is 1 to 30, an alkoxy group having a carbon number that is 1 to 30, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group; ##STR00011## wherein X.sup.1 indicates a group selected from a direct bond, O, S, SO, SO.sub.2, CO, CH.sub.2, C(CH.sub.3).sub.2 and C(CF.sub.3).sub.2, at least one of R.sup.11 to R.sup.18 is a hydroxyl group, and the others may be the same or different, indicating a group selected from a hydrogen atom, an alkyl group having a carbon number that is 1 to 30, an alkoxy group having a carbon number that is 1 to 30, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group; ##STR00012## wherein X.sup.2 and Y.sup.2 may be individually the same or different, indicating a group selected from a direct bond, O, S, SO, SO.sub.2, CO, CH.sub.2, C(CH.sub.3).sub.2 and C(CF.sub.3).sub.2, at least one of R.sup.19 to R.sup.30 is a hydroxyl group, and the others may be the same or different, indicating a group selected from a hydrogen atom, an alkyl group having a carbon number that is 1 to 30, an alkoxy group having a carbon number that is 1 to 30, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group; ##STR00013## wherein X.sup.3, Y.sup.3 and Z.sup.3 may be individually the same or different, indicating a group selected from a direct bond, O, S, SO, SO.sub.2, CO, CH.sub.2, C(CH.sub.3).sub.2 and C(CF.sub.3).sub.2, at least one of R.sup.31 to R.sup.46 is a hydroxyl group, and the others may be the same or different, indicating a group selected from a hydrogen atom, an alkyl group having a carbon number that is 1 to 30, an alkoxy group having a carbon number that is 1 to 30, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group.

5. The resin composition according to claim 1, wherein the aromatic diamine having an hydroxyl group is an aromatic diamine represented by any one of General formulas (2) to (5) below: ##STR00014## wherein at least one of R.sup.7 to R.sup.10 is a hydroxyl group, and the others may be the same or different, indicating a group selected from a hydrogen atom, an alkyl group having a carbon number that is 1 to 30, an alkoxy group having a carbon number that is 1 to 30, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group; ##STR00015## wherein X.sup.1 indicates a group selected from a direct bond, O, S, SO, SO.sub.2, CO, CH.sub.2, C(CH.sub.3).sub.2 and C(CF.sub.3).sub.2, at least one of R.sup.11 to R.sup.18 is a hydroxyl group, and the others may be the same or different, indicating a group selected from a hydrogen atom, an alkyl group having a carbon number that is 1 to 30, an alkoxy group having a carbon number that is 1 to 30, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group; ##STR00016## wherein X.sup.2 and Y.sup.2 may be individually the same or different, indicating a group selected from a direct bond, O, S, SO, SO.sub.2, CO, CH.sub.2, C(CH.sub.3).sub.2 and C(CF.sub.3).sub.2, at least one of R.sup.19 to R.sup.30 is a hydroxyl group, and the others may be the same or different, indicating a group selected from a hydrogen atom, an alkyl group having a carbon number that is 1 to 30, an alkoxy group having a carbon number that is 1 to 30, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group; ##STR00017## wherein X.sup.3, Y.sup.3 and Z.sup.3 may be individually the same or different, indicating a group selected from a direct bond, O, S, SO, SO.sub.2, CO, CH.sub.2, C(CH.sub.3).sub.2 and C(CF.sub.3).sub.2, at least one of R.sup.31 to R.sup.46 is a hydroxyl group, and the others may be the same or different, indicating a group selected from a hydrogen atom, an alkyl group having a carbon number that is 1 to 30, an alkoxy group having a carbon number that is 1 to 30, a halogen, a carboxyl group, a sulfone group, a nitro group, and a cyano group.

6. The resin composition according to claim 1, wherein the methylol-based compound is a compound having two or more groups represented by general formula (6)
CH.sub.2OR.sup.47)(6) wherein R.sup.47, in the case where a plurality of R.sup.47 exists in the compound, may be individually the same or different, indicating hydrogen or an alkyl group having a carbon number that is 1 to 10.

7. The resin composition according claim 1, wherein a content of the methylol-based compound is 1 to 20 parts by weight relative to 100 parts by weight of the polyimide-based resin.

8. The resin composition according to claim 1, wherein the acid dianhydride residue is a residue of an aromatic tetracarboxylic dianhydride.

9. A cured membrane obtained by curing the resin composition according to claim 1.

10. A laminate film obtained by laminating the resin composition according to claim 1 on at least one surface of a heat resistant insulation film.

11. The laminate film according to claim 10, wherein the surface of the heat resistant insulation film has been subjected to a mold release treatment.

12. The laminate film according to claim 10, obtained by further laminating a heat resistant insulation film having been subjected to a mold release treatment on a surface of the resin composition having been laminated on at least one surface of the heat resistant insulation film.

13. A cured membrane obtained by curing the resin composition according to claim 2.

14. A cured membrane obtained by curing the resin composition according to claim 3.

15. A cured membrane obtained by curing the resin composition according to claim 5.

Description

EXAMPLES

(1) The invention will now be illustrated with reference to Examples, but the invention is not to be limited thereto. Evaluation methods for the glass transition temperature, the weight reduction rate, and the adhesive force will be described.

(2) (1) Measurement of Glass Transition Temperature

(3) Each of tackiness agent resin solutions (AH1 to AH27) mentioned with Production examples 22 to 48 below was coated by a bar coater onto a gloss surface of an electrolytic copper foil of 18 m in thickness so that the thickness became 20 m, and then was dried at 80 C. for 10 minutes and at 150 C. for 10 minutes. Furthermore, a heating treatment was performed at 250 C. in a nitrogen atmosphere for 10 minutes for conversion into polyimide, so that tackiness agent resin-laminated copper foils were obtained. Next, the copper foil of each obtained tackiness agent resin-laminated copper foil was subjected to entire-surface etching with a ferric chloride solution to obtain a simple membrane of the tackiness agent resin.

(4) About 10 mg of each obtained simple membrane of the tackiness agent resin was loaded in a standard container made of aluminum, and was subjected to measurement (DSC method) by using a differential scanning calorimeter DSC-50 (by Shimadzu Corporation). From an inflection point of the obtained DSC curve, a glass transition temperature was calculated. After preliminary drying of 80 C.1 hour, measurement was performed at a temperature rise speed of 20 C./minute.

(5) (2) Measurement of Thermal Decomposition Start Temperature

(6) About 15 mg of each simple membrane of the tackiness agent resin obtained as described above was loaded into a standard container made of aluminum, and was subjected to measurement by using a thermogravimetric analysis apparatus TGA-50 (by Shimadzu Corporation). As for the measurement condition, the temperature was held at 60 C. for 30 minutes, and then was raised to 500 C. at a temperature rise speed of 5 C./minute.

(7) From the obtained weight reduction curve, a temperature of start of weight reduction was read out, and this temperature was determined as a thermal decomposition start temperature.

(8) (3) Measurement of Tackiness Force (Normal State)

(9) The polyimide film on a polyimide film-laminated glass substrate obtained in each of Examples and Comparative examples was provided with 10-mm-wide cutting, and a 10-mm-wide polyimide film was subjected to measurement under 90 peeling at a rate of pulling of 50 mm/minute, using a Tensilon UTM-4-100 by TOYO BOLDWIN company.

(10) (4) Measurement of Average Molecular Weight of Polysiloxane-Based Diamine and Calculation of Numerical Value n

(11) 5 g of polysiloxane-based diamine that was to be a sample was taken into a beaker, and 50 mL of a mixture solution whose IPA:toluene was 1:1 was put thereinto and dissolved. Next, using an automatic potentiometric measurement apparatus AT-610 by Kyoto Electronics Manufacturing Co., Ltd., a 0.1-N hydrochloric acid aqueous solution was dropped while stirring was being performed, to determine the amount thereof dropped to achieve the neutralization point. From the obtained amount of 0.1-N hydrochloric acid aqueous solution dropped, an average molecular weight was calculated using Expression (7) below.
2[1036.5(dropped amount (g))]/5=average molecular weight(7)
Next, the molecular weights of polysiloxane-based diamine in the case where the polysiloxane-based diamine used was n=1 and in the case where the polysiloxane-based diamine used was n=10 were calculated from the chemical structural formula, and a relation between the numerical value of n and the molecular weight was found as a relational expression of a linear function. The aforementioned average molecular weight was substituted in this relational expression to fine an average value of n.

(12) Abbreviated names for acid dianhydrides and diamines indicated Production examples below are as follows.

(13) BPDA: 3,3,4,4-biphenyl tetracarboxylic dianhydride

(14) ODPA: 3,3,4,4-diphenyl ether tetracarboxylic dianhydride

(15) BTDA: 3,3,4,4-benzophenone tetracarboxylic dianhydride

(16) APPS1: ,-bis(3-aminopropyl)polydimethyl siloxane (average molecular weight: 400, n=3 in Expression (1))

(17) APPS2: ,-bis(3-aminopropyl)polydimethyl siloxane (average molecular weight: 860, n=9 in Expression (1))

(18) APPS3: ,-bis(3-aminopropyl)polydimethyl siloxane (average molecular weight: 1600, n=19 in Expression (1))

(19) APPS4: ,-bis(3-aminopropyl)polydimethyl siloxane (average molecular weight: 3000, n=37 in Expression (1))

(20) 44DAE: 4,4-diaminodiphenyl ether

(21) APB: 1,3-bis(3-aminophenoxy)benzene

(22) 35DAP: 3,5-diaminophenol

(23) BAP: 4,4-dihydroxy-3,3-diaminophenyl propane

(24) DABS: 4,4-dihydroxy-3,3-diaminophenyl sulfone

(25) AHPB: 1,3-bis(4-amino-3-hydroxy phenyl)benzene

(26) BAHF: 4,4-dihydroxy-3,3-diaminophenyl hexafluoropropane

(27) BAHPS: bis(4-(3-amino-4-hydroxy phenoxy)benzene)sulfone

(28) 100LM: NIKALAC (registered trademark) MW-100LM (by Sanwa Chemical Col, Ltd.)

(29) MX270: NIKALAC (registered trademark) MX-270 (by Sanwa Chemical Col, Ltd.)

(30) NMP: N-methyl-2-pyrrolidone

Production Example 1 (Polymerization of Polyamide Acid Solution)

(31) After 320 g (0.8 mol) of APPS1, 20 g (0.1 mol) of 44DAE, 25.8 g (0.1 mol) of BAP were charged together with 1577 g of NMP into and were dissolved in a reaction tank equipped with a thermometer, a dry nitrogen introduction opening, a heating/cooling apparatus via warm water/cooling water, and a stirring apparatus, 310.2 g (1 mol) of ODPA was added to conduct a reaction at room temperature for 1 hour and at 60 C. for 5 hours, so that a 30-wt % polyamide acid resin solution (PA1) was obtained.

Production Examples 2 to 21 (Polymerization of Polyamide Acid Solution)

(32) 30-wt % polyamide acid resin solutions (PA2 to PA21) were obtained by performing substantially the same operation as in Production example 1, except that the kinds of acid dianhydride and diamine and the charged amounts were changed as in Table 1 and Table 2.

(33) In Production example 4, the polymerization solution gelled at the time of polymerization of polyamide acid.

(34) TABLE-US-00001 TABLE 1 upper row: composition ratio (mole %)/lower row: charged amount (g) Acid component Diamine component Solvent ODPA APPS1 APPS2 APPS3 APPS4 44DAE BAP NMP Production PA1 100 80 10 10 3154 example 1 620.4 640.0 40.0 51.6 Production PA2 100 80 10 10 2436 example 2 310.2 688.0 20.0 25.8 Production PA3 100 80 10 10 3817 example 3 310.2 1280.0 20.0 25.8 Production PA4 100 80 10 10 3216 example 4 155.1 1200.0 10.0 12.9 Production PA5 100 35 55 10 3486 example 5 620.4 602.0 220.2 51.6 Production PA6 100 45 45 10 3794 example 6 620.4 774.0 90.0 51.6 Production PA7 100 55 35 10 2051 example 7 310.2 473.0 35.0 25.8 Production PA8 100 65 25 10 2205 example 8 310.2 559.0 50.1 25.8 Production PA9 100 90 10 2590 example 9 310.2 774.0 25.8 Production PA10 100 95 10 2660 example 10 310.2 817.0 25.8 Production PA11 100 80 20 2423 example 11 310.2 688.0 40.0 Production PA12 100 80 15 5 2429 example 12 310.2 688.0 30.0 12.9 Production PA13 100 80 5 15 2443 example 13 310.2 688.0 10.0 38.8 Production PA14 100 60 15 25 2149 example 14 310.2 516.0 30.0 64.6 Production PA15 100 60 5 35 2162 example 15 310.2 516.0 10.0 90.4 Production PA16 100 55 45 2099 example 16 310.2 473.0 116.3

(35) TABLE-US-00002 TABLE 2 upper row: composition ratio (mole %)/lower row: charged amount (g) Acid component Diamine Solvent ODPA BPDA BTDA APPS2 APB DABS AHPB BAHF 35DAP BAHPS NMP Production PA17 100 80 5 15 2461 example 17 310.2 688.0 14.6 42.0 Production PA18 100 80 5 15 2439 example 18 294.2 688.0 14.6 48.6 Production PA19 100 80 5 15 2519 example 19 322.2 688.0 14.6 54.9 Production PA20 100 80 5 15 2391 example 20 322.2 688.0 14.6 18.6 Production PA21 100 80 5 15 2326 example 21 294.2 688.0 14.6 69.7

Production Example 22 (Preparation of Tackiness Agent Resin Solution)

(36) 100 g of the polyamide acid solution (PA1) obtained in Production example 1 and 5 g of 100LM, a methylol-based compound, were charged together with 11.7 g of NMP into a reaction tank equipped with a stirring apparatus, and were stirred at room temperature for 2 hours, so that a 30-wt % tackiness agent resin solution (AH1) was obtained.

Production Examples 23 to 47 (Preparation of Tackiness Agent Resin Solution)

(37) 30-wt % tackiness agent resin solutions (AH2 to 26) were obtained by performing substantially the same operation as in Production example 22, except that the kinds and charged amounts of the polyamide acid solution and the kinds and charged amounts of the methylol-based compound were changed as in Table 3.

(38) In Production examples 25, because the polyamide acid solution (PA4) had been gelled, the tackiness agent resin solution was also gelled.

(39) TABLE-US-00003 TABLE 3 Polyamide acid solution Methylol-based compound NMP Type Charged amount (g) Type Charged amount (g) (g) Production example 22 AH1 PA1 100 100LM 5 11.7 Production example 23 AH2 PA2 100 100LM 5 11.7 Production example 24 AH3 PA3 100 100LM 5 11.7 Production example 25 AH4 PA4 100 100LM 5 11.7 Production example 26 AH5 PA5 100 100LM 5 11.7 Production example 27 AH6 PA6 100 100LM 5 11.7 Production example 28 AH7 PA7 100 100LM 5 11.7 Production example 29 AH8 PA8 100 100LM 5 11.7 Production example 30 AH9 PA9 100 100LM 5 11.7 Production example 31 AH10 PA10 100 100LM 5 11.7 Production example 32 AH11 PA11 100 100LM 5 11.7 Production example 33 AH12 PA12 100 100LM 5 11.7 Production example 34 AH13 PA13 100 100LM 5 11.7 Production example 35 AH14 PA14 100 100LM 5 11.7 Production example 36 AH15 PA15 100 100LM 5 11.7 Production example 37 AH16 PA16 100 100LM 5 11.7 Production example 38 AH17 PA17 100 100LM 2 4.7 Production example 39 AH18 PA17 100 100LM 5 11.7 Production example 40 AH19 PA17 100 100LM 10 23.3 Production example 41 AH20 PA17 100 100LM 17 39.7 Production example 42 AH21 PA17 100 100LM 25 58.3 Production example 43 AH22 PA18 100 100LM 10 23.3 Production example 44 AH23 PA19 100 100LM 10 23.3 Production example 45 AH24 PA20 100 100LM 10 23.3 Production example 46 AH25 PA21 100 100LM 10 23.3 Production example 47 AH26 PA17 100 MX270 10 23.3

Example 1

(40) The tackiness agent resin solution (AH2) obtained in Production example 23 was coated onto a 0.7-mm-thick nonalkali glass substrate (by Corning company) by a spin coater with its rotation speed adjusted so that the thickness after being dried and imidized became 10 m, and was dried by performing a heat treatment at 120 C. for 10 minutes, and then was caused to undergo imidization by performing a heat treatment at 250 C. for 10 minutes, so that a tackiness agent resin-laminated glass substrate was obtained.

(41) A polyimide film (Kapton 150EN by Toray-DuPont Co., LTD.) was laid on top of the tackiness agent resin-laminated glass substrate created by the above-described method, and the polyimide film was pressure-bonded on a 160 C. hot plate by using a hand roll, so that a polyimide film-laminated glass substrate was obtained. The obtained polyimide film-laminated glass substrate was heat-treated for 15 minutes in a hot air oven set to 300 C.

(42) The post-pressure bonding and pre-heat treatment tackiness force and the post-heat treatment tackiness force of the obtained polyimide film-laminated glass substrate, and the glass transition temperature and the thermal decomposition start temperature of the tackiness agent resin were compiled in Table 4.

Example 2

(43) A polyimide film-laminated glass substrate was obtained by performing substantially the same operation as in Example 1, except that the tackiness agent resin solution was changed as in Table 4.

(44) The post-pressure bonding and pre-heat treatment tackiness force and the post-heat treatment tackiness force of the obtained polyimide film-laminated glass substrate, and the glass transition temperature and the thermal decomposition start temperature of the tackiness agent resin were compiled in Table 4.

Comparative Examples 1 to 4

(45) Polyimide film-laminated glass substrates were obtained by performing substantially the same operation as in Example 1, except that the tackiness agent resin solution was changed as in Table 4.

(46) The post-pressure bonding and pre-heat treatment tackiness forces and the post-heat treatment tackiness forces of the obtained polyimide film-laminated glass substrates, and the glass transition temperatures and the thermal decomposition start temperatures of the tackiness agent resins were compiled in Table 4.

(47) In Comparative example 2, the tackiness agent resin solution (AH4) was gelled, so that a uniform cured membrane could not be obtained.

(48) TABLE-US-00004 TABLE 4 Content of OH Parts by weight of group-containing methylol-based diamine in compound to 100 Glass Thermal decom- Tackiness force (g/cm) Tackiness polyimide Value of n parts by weight transition position start Post-pressure agent resin composition in General of polyamide temperature temperature bonding and pre- post-heat solution (mol %) formula (1) acid solution ( C.) ( C.) heat treatment treatment Example 1 AH2 10 9 5 15 >300 25 50 Example 2 AH3 10 19 5 15 >300 25 50 Comparative AH1 10 3 5 70 >300 0 example 1 Comparative AH4 10 37 5 example 2 Comparative AH11 0 9 5 10 >300 30 >500 example 3 Comparative PA17 15 9 0 10 >300 40 >500 example 4

(49) As in Examples, since the resin composition contained a polyimide-based resin and a methylol-based compound and the polyimide-based resin had a residue of a polysiloxane-based diamine where n indicate a range of 5 to 30 in General formula (1) and a residue of an aromatic diamine having a hydroxyl group, a good tackiness force was obtained after the pressure bonding, and the increase in tackiness force was small even after the 300 C. treatment, and the polyimide film, which was a base material, was able to be easily peeled off at room temperature.

(50) In Comparative examples, when either a residue of an aromatic diamine having a hydroxyl group in the polyimide-based resin or a methylol-based compound in the resin composition was absent, the adhesive force with the polyimide film that was a base material greatly increased after the 300 C. treatment, so that the polyimide film could not peeled off at room temperature. Furthermore, when n was less than or equal to 5 in the polysiloxane-based diamine represented by General formula (1), the tackiness force with the polyimide film that was a base material was substantially null. When n was greater than or equal to 30, gelation occurred during polymerization of polyamide acid, so that a uniform cured membrane could not be obtained.

Examples 3 to 8

(51) Polyimide film-laminated glass substrates were obtained by performing substantially the same operation as in Example 1, except that the tackiness agent resin solution was changed as in Table 5.

(52) The post-pressure bonding and pre-heat treatment tackiness forces and the post-heat treatment tackiness forces of the obtained polyimide film-laminated glass substrates, and the glass transition temperatures and the thermal decomposition start temperatures of the tackiness agent resins were compiled in Table 5.

(53) TABLE-US-00005 TABLE 5 Content of polysilox- Glass Thermal decom- Tackiness force (g/cm) Tackiness ane diamine in poly- transition position start Post-pressure agent resin imide composition temperature temperature bonding and pre- post-heat solution (mol %) ( C.) ( C.) heat treatment treatment Example 3 AH5 35 64 >300 2 50 Example 4 AH6 45 48 >300 10 50 Example 5 AH7 55 42 >300 15 50 Example 6 AH8 65 31 >300 25 50 Example 1 AH2 80 15 >300 25 50 Example 7 AH9 90 2 >300 25 60 Example 8 AH10 95 4 >300 15 80

(54) With regard to the polyimide-based resin contained in the resin composition, when the content of the residue of polysiloxane-based diamine in the polyimide-based resin was greater than or equal to 40 mol %, good tackiness was exhibited. Furthermore, when the content of the residue of the polysiloxane-based diamine was 60 to 90 mol %, good tackiness was exhibited, and also the increase in the tackiness force after the heat treatment was small, and good exfoliative was exhibited as well.

Examples 9 to 13

(55) Polyimide film-laminated glass substrates were obtained by performing substantially the same operation as in Example 1, except that the tackiness agent resin solution was changed as in Table 6.

(56) The post-pressure bonding and pre-heat treatment tackiness forces and the post-heat treatment tackiness forces of the obtained polyimide film-laminated glass substrates, and the glass transition temperatures and the thermal decomposition start temperatures of the tackiness agent resins were compiled in Table 6.

(57) TABLE-US-00006 TABLE 6 Polyimide composition Content of Content of OH Glass Thermal decom- Tackiness force (g/cm) Tackiness polysiloxane group-contain- transition position start Post-pressure agent resin diamine ing diamine temperature temperature bonding and pre- post-heat solution (mol %) (mol %) ( C.) ( C.) heat treatment treatment Example 9 AH12 80 5 14 >300 25 50 Example 1 AH2 80 10 15 >300 25 50 Example 10 AH13 80 15 15 >300 25 50 Example 11 AH14 60 25 37 >300 25 50 Example 12 AH15 60 35 39 >300 20 50 Example 13 AH16 55 45 48 >300 5 50

(58) With regard to the polyimide-based resin contained in the resin composition, when the content of the residue of the aromatic diamine having a hydroxyl group in the polyimide-based resin was 1 to 40 mol %, good tackiness was exhibited, and the increase in the tackiness force after the heat treatment was small, and good exfoliative was exhibited as well.

Examples 14 to 18

(59) Polyimide film-laminated glass substrates were obtained by performing substantially the same operation as in Example 1, except that the tackiness agent resin solution was changed as in Table 7.

(60) The post-pressure bonding and pre-heat treatment tackiness forces and the post-heat treatment tackiness forces of the obtained polyimide film-laminated glass substrates, and the glass transition temperatures and the thermal decomposition start temperatures of the tackiness agent resins were compiled in Table 7.

(61) TABLE-US-00007 TABLE 7 Parts by weight of Polyamide acid solution methylol-based Content of OH compound to 100 Glass Thermal decom- Tackiness force (g/cm) Tackiness group-contain- parts by weight transition position start Post-pressure agent resin ing diamine of polyamide temperature temperature bonding and pre- post-heat solution Type (mol %) acid solution ( C.) ( C.) heat treatment treatment Example 14 AH17 PA17 15 2 10 >300 40 80 Example 15 AH18 PA17 15 5 12 >300 35 40 Example 16 AH19 PA17 15 10 15 >300 30 30 Example 17 AH20 PA17 15 17 14 >300 20 20 Example 18 AH21 PA17 15 25 20 >300 5 5 Comparative PA17 PA17 15 0 10 >300 40 >500 example 4

(62) When the content of the methylol-based compound contained in the resin composition was 1 to 20 parts by weight relative to 100 parts by weight of the polyimide-based resin, good tackiness was exhibited, and the increase after the tackiness force after the heat treatment was small, and good exfoliative was exhibited as well.

Examples 19 to 23

(63) Polyimide film-laminated glass substrates were obtained by performing substantially the same operation as in Example 1, except that the tackiness agent resin solution was changed as in Table 8.

(64) The post-pressure bonding and pre-heat treatment tackiness forces and the post-heat treatment tackiness forces of the obtained polyimide film-laminated glass substrates, and the glass transition temperatures and the thermal decomposition start temperatures of the tackiness agent resins were compiled in Table 8.

(65) TABLE-US-00008 TABLE 8 Polyamide acid solution Methylol-based compound Content of OH Parts by weight Glass Thermal decom- Tackiness force (g/cm) Tackiness group-contain- to 100 parts by transition position start Post-pressure agent resin ing diamine weight of polyamide temperature temperature bonding and pre- post-heat solution Type (mol %) Type acid solution ( C.) ( C.) heat treatment treatment Example 19 AH22 PA18 15 100LM 10 18 >300 25 25 Example 20 AH23 PA19 15 100LM 10 17 >300 25 25 Example 21 AH24 PA20 15 100LM 10 17 >300 25 25 Example 22 AH25 PA21 15 100LM 10 16 >300 25 25 Example 23 AH26 PA17 15 MX270 10 15 >300 40 40

Example 24

(66) After the tackiness agent resin solution (AH19) obtained in Production example 40 was coated by a comma coater onto a polyimide film (Kapton 300H by Toray-DuPont Co., LTD.) of 100 m in thickness and 250 mm in width having been subjected to a mold release treatment with silicon resin so that the membrane thickness after the drying and imidization became 15 m, a heat treatment was performed at 120 C. for 1 minute and subsequently at 250 C. for 1 minute, so that a tackiness agent resin laminate film having a tackiness agent resin layer on one surface was obtained. Next, a PET film of 38 m in thickness and 250 mm in width having been subjected to as mold release treatment with silicone resin was laminated at 25 C. on the tackiness agent resin layer, so that a tackiness agent resin laminate film with a protective film was obtained.

(67) After the protective film-equipped tackiness agent resin laminate film obtained as described above was cut into a predetermined size, the PET film that was the protective film was peeled, and a nonalkali glass substrate (by Corning company) of 0.7 mm in thickness was placed on a hot plate whose hot plate surface temperature was set to 120 C., and the tackiness agent resin laminate film was pressure-bonded with a hand roll. Next, the polyimide film was peeled off to obtain a tackiness agent resin-laminated glass substrate. The peel surface of the peeled polyimide film was observed, and no residue of the tackiness agent resin was present on the surface.

(68) A polyimide film (Kapton 150EN by Toray-DuPont Co., LTD.) was laid on top of the tackiness agent resin-laminated glass substrate created by the above-described method, and the polyimide film was pressure-bonded at 160 C. by using a hand roll, so that a polyimide film-laminated glass substrate was obtained. The tackiness force of the obtained polyimide film-laminated glass substrate was 32 g/cm. Next, the polyimide film-laminated glass substrate was heat-treated at 300 C. for 15 minutes by using a hot air oven. The post-heat treatment tackiness force was 30 g/cm, and the polyimide film was able to be easily peeled off at room temperature.

Example 25

(69) After the tackiness agent resin solution (AH19) obtained in Production example 40 was coated by using a spin coater onto a 6-inch silicon wafer of 750 m in thickness so that the membrane thickness after the drying and imidization became 15 m, a heat treatment was performed at 140 C. for 10 minutes and subsequently at 250 C. for 30 minutes, so that a tackiness agent resin-laminated support substrate was obtained.

(70) A 6-inch silicon wafer of 750 m in thickness was stuck to the aforementioned tackiness agent resin-laminated support substrate, that is, onto the tackiness agent resin laminate, and was pressure-bonded for 120 seconds under the conditions of 200 C. and 0.5 MPa, so that a laminate of a substrate for forming a semiconductor circuit/a tackiness agent resin layer/a support substrate was obtained.

(71) The substrate for forming a semiconductor circuit of the laminate was set in a grinder DAG810 (by DISCO), and the substrate for forming a semiconductor circuit was grounded to a thickness of 100 m. After the substrate for forming a semiconductor circuit was grounded, the laminate was heat-treated at 300 C. for 1 hour. The substrate for forming a semiconductor circuit in the laminate was observed by naked eye, and none of swell, fracture, crank, etc., was present.

(72) Next, a dicing tape was stuck to the substrate for forming a semiconductor circuit by using a dicing frame, and the dicing tape surface was set on a suction pad by vacuum adsorption. Then, the support substrate was peeled off by picking up a portion of the support substrate at room temperature. The substrate for forming a semiconductor circuit had no fracture, crack, etc.

Example 26

(73) A 6-inch silicon wafer of 750 m in thickness was used. The PET film that was a protective film of the protective film-equipped tackiness agent resin laminate film manufactured in Example 24 was peeled off, and then the 6-inch silicon wafer of 750 m in thickness was placed on a hot plate whose hot plate surface temperature was set to 120 C., and the tackiness agent resin laminate film was pressure-bonded by a hand roll. Next, the polyimide film was peeled off, and a heat treatment was performed at 250 C. for 30 minutes, so that a tackiness agent resin-laminated support substrate was obtained.

(74) After that, substantially the same operation as in Example 25 was performed. After the support substrate was peeled, the substrate for forming a semiconductor circuit did not have a fracture, a crack, etc.